US2862885A - Foam inhibition in hydrocarbon oils - Google Patents
Foam inhibition in hydrocarbon oils Download PDFInfo
- Publication number
- US2862885A US2862885A US482657A US48265755A US2862885A US 2862885 A US2862885 A US 2862885A US 482657 A US482657 A US 482657A US 48265755 A US48265755 A US 48265755A US 2862885 A US2862885 A US 2862885A
- Authority
- US
- United States
- Prior art keywords
- foam
- oil
- petroleum
- oils
- employed
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229930195733 hydrocarbon Natural products 0.000 title claims description 22
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 19
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 16
- 239000003921 oil Substances 0.000 title description 39
- 239000006260 foam Substances 0.000 title description 22
- 230000005764 inhibitory process Effects 0.000 title 1
- 229920001519 homopolymer Polymers 0.000 claims description 24
- -1 VINYL GROUP Chemical group 0.000 claims description 10
- 229920000642 polymer Polymers 0.000 description 22
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 20
- 238000005187 foaming Methods 0.000 description 16
- 239000000463 material Substances 0.000 description 15
- 239000003208 petroleum Substances 0.000 description 14
- 238000006116 polymerization reaction Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- 239000000178 monomer Substances 0.000 description 12
- 239000000654 additive Substances 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 10
- 229920001296 polysiloxane Polymers 0.000 description 10
- 239000010687 lubricating oil Substances 0.000 description 8
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000002518 antifoaming agent Substances 0.000 description 6
- 239000003599 detergent Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 5
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 4
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- IRTACFOVZDBFEX-UHFFFAOYSA-N ethenyl-diethoxy-ethylsilane Chemical compound CCO[Si](CC)(C=C)OCC IRTACFOVZDBFEX-UHFFFAOYSA-N 0.000 description 3
- 239000000787 lecithin Substances 0.000 description 3
- 229940067606 lecithin Drugs 0.000 description 3
- 235000010445 lecithin Nutrition 0.000 description 3
- 230000001050 lubricating effect Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000001629 suppression Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- URZLRFGTFVPFDW-UHFFFAOYSA-N ethenyl-diethoxy-phenylsilane Chemical compound CCO[Si](OCC)(C=C)C1=CC=CC=C1 URZLRFGTFVPFDW-UHFFFAOYSA-N 0.000 description 2
- GGJQEMXRDJPGAH-UHFFFAOYSA-N ethenyl-ethoxy-diphenylsilane Chemical compound C=1C=CC=CC=1[Si](C=C)(OCC)C1=CC=CC=C1 GGJQEMXRDJPGAH-UHFFFAOYSA-N 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000010688 mineral lubricating oil Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- BYTCDABWEGFPLT-UHFFFAOYSA-L potassium;sodium;dihydroxide Chemical compound [OH-].[OH-].[Na+].[K+] BYTCDABWEGFPLT-UHFFFAOYSA-L 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 239000005069 Extreme pressure additive Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001279 adipic acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000002877 alkyl aryl group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001536 azelaic acids Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000007799 cork Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- COYNRSOPBZWWST-UHFFFAOYSA-N dibutyl-ethenyl-ethoxysilane Chemical compound CCCC[Si](C=C)(OCC)CCCC COYNRSOPBZWWST-UHFFFAOYSA-N 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- ZGIFOQQSVIUQIU-UHFFFAOYSA-N diethoxy(hex-5-enyl)silane Chemical compound C(=C)CCCC[SiH](OCC)OCC ZGIFOQQSVIUQIU-UHFFFAOYSA-N 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- YTUPSNLWAAEFPL-UHFFFAOYSA-N ethenyl(ethoxy)silane Chemical class CCO[SiH2]C=C YTUPSNLWAAEFPL-UHFFFAOYSA-N 0.000 description 1
- MBGQQKKTDDNCSG-UHFFFAOYSA-N ethenyl-diethoxy-methylsilane Chemical compound CCO[Si](C)(C=C)OCC MBGQQKKTDDNCSG-UHFFFAOYSA-N 0.000 description 1
- 239000012208 gear oil Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- NUMNZKICGJJSHN-UHFFFAOYSA-N phenyl octadecanoate Chemical class CCCCCCCCCCCCCCCCCC(=O)OC1=CC=CC=C1 NUMNZKICGJJSHN-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 230000003449 preventive effect Effects 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003330 sebacic acids Chemical class 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- SGCFZHOZKKQIBU-UHFFFAOYSA-N tributoxy(ethenyl)silane Chemical compound CCCCO[Si](OCCCC)(OCCCC)C=C SGCFZHOZKKQIBU-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/28—Organic compounds containing silicon
- C10L1/285—Organic compounds containing silicon macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M1/00—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants
- C10M1/08—Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants with additives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/024—Propene
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
- C10M2205/026—Butene
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2207/129—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of thirty or more carbon atoms
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/34—Esters having a hydrocarbon substituent of thirty or more carbon atoms, e.g. substituted succinic acid derivatives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/109—Polyethers, i.e. containing di- or higher polyoxyalkylene groups esterified
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
- C10M2219/088—Neutral salts
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
- C10M2219/089—Overbased salts
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2225/00—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2225/04—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions obtained by phosphorisation of macromolecualr compounds not containing phosphorus in the monomers
- C10M2225/041—Hydrocarbon polymers
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2227/00—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions
- C10M2227/04—Organic non-macromolecular compounds containing atoms of elements not provided for in groups C10M2203/00, C10M2207/00, C10M2211/00, C10M2215/00, C10M2219/00 or C10M2223/00 as ingredients in lubricant compositions having a silicon-to-carbon bond, e.g. organo-silanes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2010/00—Metal present as such or in compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/08—Hydraulic fluids, e.g. brake-fluids
Definitions
- This invention relates to the prevention of excessive foaming of petroleum-type oils, especially those in the lubricating oil viscosity range.
- it relates to petroleum-type products which have been rendered nonfoaming by the addition of minute amounts of polymers of vinylalkoxysilanes or vinylalkylalkoxysilanes.
- R groups are either hydrogen or hydrocarbon radicals and x is a positive integer.
- silicones generally possess thermal stability far in excess of hydrocarbons they lack much of the lubricating properties of oils derived directly from petroleum or synthetic polymers of the petroleum type. On the other hand, although a minute amount of certain silicones will suppress foaming of various petroleum stocks, hydrocarbons have no such ability.
- novel polyvinylalkoxysilanes and polyvinylalkylalkoxy silanes described and claimed in the copending application of Bailey and Mixer for Letters Patent, Serial No. 374,137, filed August 13, 1953, now U. S. Patent No. 2,777,869, have been found to have exceptional foam inhibiting properties. These homopolymers and the method' of preparation are also described in an article by Wagner et al. in Industrial and Engineering Chemistry 45, 367-373 195 3).
- n is a positive integer greater than one and R, R x and y are as above defined.
- vinylalkoxysilanes as employed herein refers to compounds containing at least one alkoxy radical attached to the pendant silicon atom and will therefore include vinylalkylalkoxysilanes.
- homopolymers of the type herein described differ from other vinyl siloxane polymers in that polymerization occurs through the vinyl group to produce basic carbon to carbon chains, rather than through the silicon and oxygen atoms to yield the alternate silicon-oxygen type chain.
- the homopolymers contain at least one long hydrocarbon chain, which contributes to substantially greater compatability with organic liquids such as petroleum oils and the like.
- the polymerization process required to prepare the homopolymers useful in accordance herewith is a conventional vinyl-type polymerization employing the specified catalyst, di-t-butyl peroxide with heating until polymerization occurs.
- the polymerization be conducted in an inert, substantially anhydrous atmosphere.
- an inert atmosphere such as nitrogen, argon, carbon dioxide or other inert gas be maintained over the reaction mixture during polymerization.
- the concentration of the catalyst and the temperature of polymerization also have an eifect on polymer prop erties. And in general it may be said that polymer viscosity will increase as catalyst concentration is increased until an optimum concentration is reached. At low catalyst concentrations the polymer viscosity increases with increasing polymerization temperature but at higher catalyst concentrations the polymer viscosity appears to decrease with increasing polymerization temperature.
- the range of molecular weight of the herein described polymers within which the anti-foam properties are exhibited to the greatest extent is from about 325 to about 8,000 and preferably from about 3,000 to about 8,000. Polymers having a molecular weight higher than about 8,000 may, of course be employed. When higher molecular weight polymers are employed, for example in the upper range recited, it has been found that a somewhat smaller amount of the polymer is required to obtain desirable foam suppression. Thus, in the range of from about 3,000 to about 8,000 molecular weight, the quantity of polymer employed may vary from as little as 2 parts per million (p. p. m.) to a considerably larger amount, the upper limit ordinarily being determined by economic considerations. In the molecular weight range below about 3,000 it is preferred to employ at least about 50 p. p. m. of a polymer and more if economics permit.
- R represents a monovalent hydrocarbon radical, e.. g. alkyl, cycloalkyl, aryl, alkylaryl or aralkyl containing from 1 to about 18 carbon atoms and preferably from 2 to about 8 carbon atoms
- R may be an alkyl radical containing from 2 to about 18 carbon atoms and preferably from 2 to about 8.
- the method employed to evaluate the effectiveness of the compounds of the present invention in the suppression of foam is outlined below. It is essentially the ASTM test D-892-46T. In this test the test sample at room temperature (ca. 80 F.) was poured into a 1,000 ml. cylinder until the liquid level was at the 190 ml. mark. The air inlet tube with an attached diffuser stone was then inserted into the oil and after five minutes the air was turned on at the rate of about 95 ml. per minute. The air was introduced for five minutes and at the end of that time it was turned off and the level to which the foam above the liquid had risen in the cylinder was immediately recorded. The foam was then allowed to stand for an additional ten minutes and the volume of foam again recorded.
- the so-called reference oil or control referred to in the following Table H was prepared by adding 0.3% of lecithin to petroleum oils free of additives.
- the lecithin promotes foaming.
- the various anti-foam additives tested were added to the reference oil as a 1% (grams per volume) solution in toluene or kerosene.
- the anti-foam concentrate was added dropwise to the mechanically stirred oil at about 140 F. with the stirring being continued for approximately ten minutes after addition of the foam-suppressing additive.
- Typical of the vinylalkoxysilanes which may be employed to produce polymers suitable for foam suppression in accordance herewith are vinyltriethoxysilane, vinyltributoxysilane, vinylbutyldiethoxysilane, vinyldibutylethoxysilane, vinylhexyldibutoxysilane, vinyldecyldipentoxysilane, vinylphenyldiethoxysilane, vinyldiphenyl Synthesis of homopolymers of the type described above is exemplified by the following examples which, of course, are set forth for purposes of explanation and illustration and not of limitation. It will be noted in this connection, that Example 2 is concerned with the preparation of a number of difierent vinyl ethoxysilanes.
- Example 1 Di-t -b'utyl peroxide (0.50 gram) was diluted to25.0 ml. with purified vinyltriethoxsilane in a Norm'ax volumetric flask to form a catalyst solution. Then 215ml. of purified vinylthiethoxsilane (B. P. 158 F. at 30 mm. Hg; 11 1.3966, (1 4 0.9036; MR calculated 50.61; observed, 56.66; infrared spectrum No. 61-9, efilux time unheated 16.4 seconds in tube A) and 1.00 inlf'jof the catalyst solution were placed in a rigorously cleaned, 25 mm. x 200 mm.
- Example 2 The homopolymerization of the vinylalkoxysilanes also occurs when a monovalent hydracarbon radical, such as an aryl or alkyl radical, replaces one or two of the alkoxy groups.
- a monovalent hydracarbon radical such as an aryl or alkyl radical
- the physical properties of the vinyldiphe'nylethoxysilane monomer were: B. P. 298 F. at 5.0 mm. Hg; 11 1.5504; (1254 1.0169; MR observed, 79.73, calculated 79.47.
- samples of vinyldiphenylethoxysilane con-- taining 1% di-t-butyl peroxide were heated for 16 hours at 239 F., the product was a plastic solid; when heated for 16 hours at 302 F., the product was a brittle solid; and when heated for 144 hours at 212 F., the product was a viscous liquid having an efllux time in tube A 18,200 seconds.
- foam-suppressing additives herein described may be employed in petroleum oils generally and in lubricating oils particularly which contain additional additives.
- lubricating oils generally contain one or more of the following types of additives, viz., extreme pressure additives, viscosity indexed improvers, oiliness agents, detergents, etc. It is in connection with detergents particularly that foam-suppressing additives of the type described will find particular utility inasmuch as oils containing the same have a greater tendency toward foaming.
- one of the best known and most Widely used types of petroleum detergents are the phosphorus and sulphur-containing materials prepared by reaching the phosphorous sulphide with a hydrocarbon such as a butylene polymer and then neutralizing the same with sodium potassium hydroxide orthe like.
- Other detergent type additives commonly employed in lubricating oils are the alkaline earth petroleum sulfonates, the alkaline earth phenyl stearates, the alkaline earth alkyl phenol sulphides, etc.
- the anti-foam agents of the present invention may, of Course, be employed in lubricating oils containing detergent materials such as these as well as various other detergent additives not herein enumerated.
- oils of the petroleum type which are commonly employed as substitutes for petroleum oils, particularly in lubricating or hydraulic applications, may be inhibited against foaming by the use of the polymers herein described.
- These include polymeric hydocarbons resulting from the polymerization of various unsaturated hydrocarbons, e. g. polybutenes, polypropylene mixtures of these, etc. oleaginous materials of the polyalkylene oxide type (polyalkylene glycols, esters thereof, etc.) e.
- the so-called Ucon oils marketed by Carbide & Carbon Corporation aliphatic diesters of dicarboxylic acids such as the butyl, hexyl, Z-ethyl-hexyl, decyl, lauryl, etc. esters of such acids as sebacic acids, adipic acids, azelaic acids, etc.
- the term petroleum-type oil as employed in the appended claims shall be understood to include not only the hydrocarbon oils derived directly from petroleum but other organic liquids having a basic carbon-hydrogen structure and having many of the properties of petroleum hydrocarbons such as those above enumerated.
- oil as employed herein and in the claims is used in its broadest sense.
- nonoleaginous materials such as gasoline, kerosene and similar materials, to the extent that such materials may be improved in their foaming characteristics by the addition thereto of the polymers herein described, are included within the meaning of the term oil as employed in the claims.
- a mineral lubricating oil containing from about 2 parts per million to about 50 parts per million of homopolymer of a monovinylalkoxysilane which had been polymerized through the vinyl group to a material having a molecular weight from about 3000 to about 8000.
- the method of suppressing foaming of hydrocarbon oils which comprises admixing with said oil a minor amount sufiicient to inhibit foam of a homopolymer of monovinylalkoxysilane which had been polymerized in the presence of di-t-butyl peroxide through the vinyl group to a clear light colored product.
- a mineral lubricating oil containing from about 2 parts per million to about 50 parts per million of homopolymer of a monovinylalkoxysilane which had been polymerized through the vinyl group to a material having a molecular weight from about 325 to about 8000.
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Description
States 2,862,885 FOAM rwrnBrrioN IN HYDROCARBON orrs' Rudolph S. Nelson, Larchmont, and Charles W. West,
Kenmore, N. Y., assignors to Union Carbide Corporation, a corporation of New York No Drawing. Application January 18, 1955 Serial No. 482,657
11 Claims. (Cl. 25249.6)
This invention relates to the prevention of excessive foaming of petroleum-type oils, especially those in the lubricating oil viscosity range. In particular it relates to petroleum-type products which have been rendered nonfoaming by the addition of minute amounts of polymers of vinylalkoxysilanes or vinylalkylalkoxysilanes.
It is the principal object of this invention to suppress foaming in petroleum-type oils and particularly mineral v.oils in the lubricating oil viscosity range. A further object is to provide the art with novel anti-foam additives of exceptional effectiveness. These and additional objects and advantages of the present invention will be apparent from the following detailed description.
Various members of the family of organic compounds referred to generically as silicones or polysiloxanes have been found useful as foam depressors or preventives.
.Silicones, generally speaking, have a chemical structure .of the type:
wherein the R groups are either hydrogen or hydrocarbon radicals and x is a positive integer. While the silicones generally possess thermal stability far in excess of hydrocarbons they lack much of the lubricating properties of oils derived directly from petroleum or synthetic polymers of the petroleum type. On the other hand, although a minute amount of certain silicones will suppress foaming of various petroleum stocks, hydrocarbons have no such ability. For these as well as other reasons it may' novel polyvinylalkoxysilanes and polyvinylalkylalkoxy silanes described and claimed in the copending application of Bailey and Mixer for Letters Patent, Serial No. 374,137, filed August 13, 1953, now U. S. Patent No. 2,777,869, have been found to have exceptional foam inhibiting properties. These homopolymers and the method' of preparation are also described in an article by Wagner et al. in Industrial and Engineering Chemistry 45, 367-373 195 3).
One of the most vexing foaming problems encountered with petroleum and its products is the foaming of lubricating oils in engines, turbines, etc. On the other hand the foaming of petroleum-type oils generally when poured into a tank car or even a smaller container is a source of considerable concern. Foaming of a lubricating oil results in an inadequate lubricating film over the moving parts and a consequent reduction in effectiveness of the oil.
foaming of oil products during filling of shipping con- 2,862,885 Patented Dec. 2, 1958 tainers of various sizes results either in waste of valuable container capacity or loss of an excessive amount of time waiting for the foam to subside. The two foaming prob- I vinylalkoxysilanes, which may be polymerized through the vinyl groups to produce so-called homopolymers, in
the presence of a peroxide may be represented by the formula:
(R)eSi(OR where R is a monovalent hydrocarbon radical, R is an alkyl radical including alkoxyalkyl, x is 0, 1 or 2, and y is 1, 2 or 3, the sum of x and y being 3. These compounds may be employed in the production of the novel foam inhibitors of the present invention. As indicated above, the polymerization of such silanes by the process described in copending Serial No. 374,137 takes place at the vinyl groups and results in homopolymers of the general structure:
where n is a positive integer greater than one and R, R x and y are as above defined. It will be understood that the term vinylalkoxysilanes as employed herein refers to compounds containing at least one alkoxy radical attached to the pendant silicon atom and will therefore include vinylalkylalkoxysilanes.
It isimportant to recognize that the homopolymers of the type herein described differ from other vinyl siloxane polymers in that polymerization occurs through the vinyl group to produce basic carbon to carbon chains, rather than through the silicon and oxygen atoms to yield the alternate silicon-oxygen type chain. As a result the homopolymers contain at least one long hydrocarbon chain, which contributes to substantially greater compatability with organic liquids such as petroleum oils and the like.
Although the method whereby the above-described homopolymers are produced is not part of the present invention inasmuch as that subject matter is described and claimed in the aforementioned copending application, it is important to prepare these homopolymers carefullyand in accordance with the method of the aforementioned application. The polymerization of vinylalkoxysilanes has been suggested in the prior art by other methods but these result only in residue polymers which are brittle resins of a brown to black color and the method prescribed for use in accordance herewith results in true homopolymers which are colorless to light colored products and range from viscous liquids to gummy or plastic solids. In this connection it should be noted that the polymerization of vinylalkoxysilanes to such desirable products requires the use of highly pure monomers and a very specific catalyst, viz., di-t-butyl peroxide, which is markedly effective in the production of viscous polymers.
The polymerization process required to prepare the homopolymers useful in accordance herewith is a conventional vinyl-type polymerization employing the specified catalyst, di-t-butyl peroxide with heating until polymerization occurs. In addition, however, to the requirement for a specific catalyst and the necessity of employing the pure monomer it is preferred that the polymerization be conducted in an inert, substantially anhydrous atmosphere. The presence of oxygen, air or substantial amounts of moisture is undesirable, as polymer viscosity is reduced thereby. However, some degree of polymerization will occur even under these adverse conditions but it is certainly more desirable and preferred for use in accordance herewith that an inert atmosphere such as nitrogen, argon, carbon dioxide or other inert gas be maintained over the reaction mixture during polymerization.
The concentration of the catalyst and the temperature of polymerization also have an eifect on polymer prop erties. And in general it may be said that polymer viscosity will increase as catalyst concentration is increased until an optimum concentration is reached. At low catalyst concentrations the polymer viscosity increases with increasing polymerization temperature but at higher catalyst concentrations the polymer viscosity appears to decrease with increasing polymerization temperature. These effects are shown in the following table:
TABLE I.EFFECT OF TEMPERATURE AND CATALYST 31450 IIIIIIIIII IIIIIIIII 239 239 302 Reaction time ..hr. 16 64 10 1 This product was stripped of 3 wt. percent lights after which it was too viscous for the test.
The range of molecular weight of the herein described polymers within which the anti-foam properties are exhibited to the greatest extent is from about 325 to about 8,000 and preferably from about 3,000 to about 8,000. Polymers having a molecular weight higher than about 8,000 may, of course be employed. When higher molecular weight polymers are employed, for example in the upper range recited, it has been found that a somewhat smaller amount of the polymer is required to obtain desirable foam suppression. Thus, in the range of from about 3,000 to about 8,000 molecular weight, the quantity of polymer employed may vary from as little as 2 parts per million (p. p. m.) to a considerably larger amount, the upper limit ordinarily being determined by economic considerations. In the molecular weight range below about 3,000 it is preferred to employ at least about 50 p. p. m. of a polymer and more if economics permit.
ethoxsilane, vinylethyldiethoxysilane, vinylmethyldiethoxysilane, etc. Thus, in the general formulawherein R represents a monovalent hydrocarbon radical, e.. g. alkyl, cycloalkyl, aryl, alkylaryl or aralkyl containing from 1 to about 18 carbon atoms and preferably from 2 to about 8 carbon atoms, and R may be an alkyl radical containing from 2 to about 18 carbon atoms and preferably from 2 to about 8.
The method employed to evaluate the effectiveness of the compounds of the present invention in the suppression of foam is outlined below. It is essentially the ASTM test D-892-46T. In this test the test sample at room temperature (ca. 80 F.) was poured into a 1,000 ml. cylinder until the liquid level was at the 190 ml. mark. The air inlet tube with an attached diffuser stone was then inserted into the oil and after five minutes the air was turned on at the rate of about 95 ml. per minute. The air was introduced for five minutes and at the end of that time it was turned off and the level to which the foam above the liquid had risen in the cylinder was immediately recorded. The foam was then allowed to stand for an additional ten minutes and the volume of foam again recorded. If the foam collapsed entirely within ten minutes, nil foam would be noted. Following this a second sample of the oil being tested was placed in a clean 1,000 ml. cylinder and the test was repeated as before, with the exception that a temperature of 200 F. (obtained by means of a constant temperature bath) instead of room temperature was employed.
The so-called reference oil or control referred to in the following Table H was prepared by adding 0.3% of lecithin to petroleum oils free of additives. The lecithin, of course, promotes foaming. The various anti-foam additives tested, the results of which are reflected in the following table, were added to the reference oil as a 1% (grams per volume) solution in toluene or kerosene. And the anti-foam concentrate was added dropwise to the mechanically stirred oil at about 140 F. with the stirring being continued for approximately ten minutes after addition of the foam-suppressing additive. Results of a series of tests based upon the above procedure in which reference oils containing an additive of the present invention are compared with the reference oil free of any foamsuppressor and the reference oil containing varying amounts of a well known silicone type foam suppressor, viz., dimethyl silicone.
TABLE II Foam volume at room Foam volume at temp. 200 F. Conc., Antifoam composition p. p. 111.
After After 10 min. After After 10 min. 5 min. settling 1 5 min. settling I bubbling bubbling Reference oil alone (Sinclair Opallne gear oil 1,000 SUS at 100 F.
base plus 0.3% lecithin) I 570 530 565 0 (6 min. Ref. plus dimethyl silicone, 350 cs 10 90 30 410 0 (3 min. Do 10 0 (3 min.) 230 0 (2 min. Ref. plus dimethyl silicone, 1,000 cs 10 0 0 10 0 1 min. Ref. plus dimethyl silicone, 10,000 cs 10 0 0 10 0 1 min. Ref. plus polyvlnyl-triethoxysilane (325 M. W.) 10 530 480 430 0 (5 min.) Do 50 10 0 (2 mln.; 0 0 Ref. plus polyvinyl-triethoxysilane (5,000 M. W.) 10 10 0 0 0 -g Ref. plus polyviuyl-triethoxysilane (5,700 M. W.) 10 0 0 10 0 1 min. Ref. plus polyvinyl-triethoxysilane (7,820 M. W.) 10 10 0 1 min.) 10 0 1 miIL;
Do 5 10 0 (3 min.) 20 0 1 min.
1 Times given parenthetically pertain to complete collapse of foam. 2 Gliddol R, commercial product of Glidden Corporation.
Typical of the vinylalkoxysilanes which may be employed to produce polymers suitable for foam suppression in accordance herewith are vinyltriethoxysilane, vinyltributoxysilane, vinylbutyldiethoxysilane, vinyldibutylethoxysilane, vinylhexyldibutoxysilane, vinyldecyldipentoxysilane, vinylphenyldiethoxysilane, vinyldiphenyl Synthesis of homopolymers of the type described above is exemplified by the following examples which, of course, are set forth for purposes of explanation and illustration and not of limitation. It will be noted in this connection, that Example 2 is concerned with the preparation of a number of difierent vinyl ethoxysilanes.
Example 1 Di-t -b'utyl peroxide (0.50 gram) was diluted to25.0 ml. with purified vinyltriethoxsilane in a Norm'ax volumetric flask to form a catalyst solution. Then 215ml. of purified vinylthiethoxsilane (B. P. 158 F. at 30 mm. Hg; 11 1.3966, (1 4 0.9036; MR calculated 50.61; observed, 56.66; infrared spectrum No. 61-9, efilux time unheated 16.4 seconds in tube A) and 1.00 inlf'jof the catalyst solution were placed in a rigorously cleaned, 25 mm. x 200 mm. Pyrex test tube flushed with argon and equipped with a well-fitting cork. Thus the contents of the tube were 22.5 ml. (20.0 grams) of vinyltriethoxysilane and 0.02 gram (or 0.10 weight percent of di-t-butyl peroxide. The contents were shaken and then the space above the contents again flushed with argon. The contents and test tube were heated in a constant temperature oil bath at 239 F. for 16 hours. The polymerized material was stripped of monomer by heating at 239 F. for 16 hours. The polymerized material was stripped of monomer by heating at 239 F. and 1 mm. Hg absolute pressure until nor more monomer was removed (about 1 hour). Approximately 0.5 gram of monomer was removed indicating a 97% conversion. The resulting product was a clear, colorless, very viscous liquid having the following physical properties: n =1.4445 d 4=0.97 to 1.00 Infrared spectrum No. 621 Efliux time in tube C 570 seconds Effiux time extrapolated to tube A 65,000 seconds The product was examined by infrared absorption and the several absorption bands accepted as signifying the presence of the vinyl (C=C) double bond were shown to be missing. This proves that the vinyl group has reacted.
INFRARED ANALYSIS Bands Probable Assignment Monomer Polymer 3. 27 u. Missing" 'O-'H stretch in vinyl group. 6. 22 do C=C stretch in vinyl group.- 7. 09 Reduced. CH2 deformation in vinyl group (sym.
in-plane). 7. 83 [L- Missing CH1 deformation in vinyl group (inp an 9.88 1. do CH1 deformation in vinyl group (out-oip ane 10.38 p. OH deformation in vinyl group (out-ofplane) plus Si-O-C vibration. 10. 45 n Si-O-G vibration (less intense than combined band at 10.38 in monomer).
Example 2 The homopolymerization of the vinylalkoxysilanes also occurs when a monovalent hydracarbon radical, such as an aryl or alkyl radical, replaces one or two of the alkoxy groups. Thus vinylethyldiethoxysilane, vinylphenyldiethoxysilane and vinyldiphenylethoxysilane were polymerized under conditions tabulated below by heating for 16 hours at 239 F.
TABLE III.-HOMOPOLYMERIZATION OF OTHER VINYLETHOXYSILANES Product efilux Time in seconds Expt. Di-t-butyl peroxide conc.
No. Monomer 0.02 0.10 0.5
None weight weight weight percent percent percent (a) Vinyltriethoxysilane 19.4 136 36,000 66,000 Vinylethyldiethoxysilane. 17.2 18.8 25 6,000 (c) Vinylphcnyldicthoxysi- 19.3 23.2 33.1 134,000
ne. (d) vilnyldiphenylethoxysi- 23.2 27.7 36.0 8,870
ane.
1 Efliux time measured in Tube A. 2 Extrapolated values from times measured in Tube 0.
The physical properties of the vinyldiphe'nylethoxysilane monomer were: B. P. 298 F. at 5.0 mm. Hg; 11 1.5504; (1254 1.0169; MR observed, 79.73, calculated 79.47. When samples of vinyldiphenylethoxysilane con-- taining 1% di-t-butyl peroxide were heated for 16 hours at 239 F., the product was a plastic solid; when heated for 16 hours at 302 F., the product was a brittle solid; and when heated for 144 hours at 212 F., the product Was a viscous liquid having an efllux time in tube A 18,200 seconds.
Although the description hereinabove set forth of the type of monomer which may be employed to produce foam-suppressing polymers falling within the scope of the present invention has been limited to vinyl derivatives, it should be understood that homopolymers or copolymers of alkenylalkoxysilanes generally may be employed in accordance herewith. Thus polymers of allylalkoxysilanes and cyclohexenylalkoxysilanes may also be employed.
It should be understood further that the foam-suppressing additives herein described may be employed in petroleum oils generally and in lubricating oils particularly which contain additional additives. Thus, for example, lubricating oils generally contain one or more of the following types of additives, viz., extreme pressure additives, viscosity indexed improvers, oiliness agents, detergents, etc. It is in connection with detergents particularly that foam-suppressing additives of the type described will find particular utility inasmuch as oils containing the same have a greater tendency toward foaming. In this connection one of the best known and most Widely used types of petroleum detergents are the phosphorus and sulphur-containing materials prepared by reaching the phosphorous sulphide with a hydrocarbon such as a butylene polymer and then neutralizing the same with sodium potassium hydroxide orthe like. Other detergent type additives commonly employed in lubricating oils are the alkaline earth petroleum sulfonates, the alkaline earth phenyl stearates, the alkaline earth alkyl phenol sulphides, etc. The anti-foam agents of the present invention may, of Course, be employed in lubricating oils containing detergent materials such as these as well as various other detergent additives not herein enumerated.
It should be further understood that the invention is not limited to the prevention of foaming of petroleum oils. Thus, oils of the petroleum type which are commonly employed as substitutes for petroleum oils, particularly in lubricating or hydraulic applications, may be inhibited against foaming by the use of the polymers herein described. These include polymeric hydocarbons resulting from the polymerization of various unsaturated hydrocarbons, e. g. polybutenes, polypropylene mixtures of these, etc. oleaginous materials of the polyalkylene oxide type (polyalkylene glycols, esters thereof, etc.) e. g., the so-called Ucon oils marketed by Carbide & Carbon Corporation; aliphatic diesters of dicarboxylic acids such as the butyl, hexyl, Z-ethyl-hexyl, decyl, lauryl, etc. esters of such acids as sebacic acids, adipic acids, azelaic acids, etc. Accordingly, the term petroleum-type oil as employed in the appended claims shall be understood to include not only the hydrocarbon oils derived directly from petroleum but other organic liquids having a basic carbon-hydrogen structure and having many of the properties of petroleum hydrocarbons such as those above enumerated.
Moreover, the term oil as employed herein and in the claims is used in its broadest sense. Thus, nonoleaginous materials such as gasoline, kerosene and similar materials, to the extent that such materials may be improved in their foaming characteristics by the addition thereto of the polymers herein described, are included within the meaning of the term oil as employed in the claims.
Having thus described our invention, what we claim as novel and desire to protect by Letters Patent is set forth in the following claims: 1
1. A hydrocarbon oil containing a minor amount sufiicient to inhibit foam' of a homopolymer of a monovinylalkoxysilane having a molecular weight of at least about 325 which had been polymerized through the vinyl group.
2. A hydrocarbon oil containing from about 2 parts per million to about 50 parts per million of a homopolymer of a monovinylalkoxysilane which had been polymerized through the vinyl group to a material of from about 325 to about 8000 molecular weight.
3. A hydrocarbon oil containing from about 2 parts per million to about 50 parts per million of a homopolymer of a monovinylalkoxysilane which had been polymerized through the vinyl group to a material of from about 3000 to about 8000 molecular weight.
4. A mineral lubricating oil containing from about 2 parts per million to about 50 parts per million of homopolymer of a monovinylalkoxysilane which had been polymerized through the vinyl group to a material having a molecular weight from about 3000 to about 8000.
5. A petroleum hydrocarbon fraction containing a minor amount sufficient to inhibit foam of homopolymer of a monovinylalkoxysilane which had been polymerized through the vinyl group to a material having a molecular weight of from about 325 to about 8000, said monovinyl-alkoxysilane having the general formula:
(R),-Si(OR wherein R is a monovalent hydrocarbon radical, R is an alkyl radical, x is selected from the group consisting of 0, 1 and 2, y is a positive integer from 1 to 3, both inclusive, and x+y=3.
6. A petroleum hydrocarbon fraction containing a minor amount sufiicient to inhibit foam of homopolymer of monovinylalkoxysilane which had been polymerized through the vinyl group to a material having a molecular weight of from about 325 to about 8000, said monovinylalkoxysilane having the general formula:
orrr=cn (R)=-S i(OR wherein R is a monovalent hydrocarbon radical containing from 1 to about 18 carbon atoms, R is an alkyl radical containing from 1 to about 18 carbon atoms x is selected from the group consisting of 0, 1 and 2, y is a positive integer from 1 to 3, both inclusive, and x+y=3. 7. The method of suppressing foaming of hydrocarbon oils which comprises admixing with said oil a minor amount sufiicient to inhibit foam of a homopolymer of monovinylalkoxysilane which had been polymerized in the presence of di-t-butyl peroxide through the vinyl group to a clear light colored product.
8. The method of claim 7 wherein the amount of homopolymer admixed with said hydrocarbon oil is from about 2 parts per million to about 50 parts per million.
9. The method of claim 7 wherein the homopolymer admixed with said hydrocarbon oil is prepared from vinyltriethoxysilane.
10. The method of suppressing foaming of a hydrocarbon oil which comprises admixing with said hydrocarbon oil a minor amount of a homopolymer of a vinylalkoxysilane having a molecular weight of at least about 325 which homopolymers were prepared by heating a vinylalkoxysilane of the structure- CHFCH R)u where R is a monovalent hydrocarbon radical, R is an alkyl radical, x is selected from the group consisting of 0, 1 and 2, y is a positive integer from 1 to 3, both inclusive, and x+y=3, in the presence of di-t-butyl peroxide.
11. A mineral lubricating oil containing from about 2 parts per million to about 50 parts per million of homopolymer of a monovinylalkoxysilane which had been polymerized through the vinyl group to a material having a molecular weight from about 325 to about 8000.
OTHER REFERENCES Wagner et al.: Ind. and Eng. Chem, vol. 45, 1953, pp. 367-373.
UNITED STATES PATENT OFFICE Certificate of Correction Patent No. 2,862,885 December 2, 1958 Rudolph S. Nelson et a1.
It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.
Column 5, line 5, for "vinylthiethoxsilane read vinyltriethoxysilane; line 7, for 56.68 read 50.66; lines 17 to 19, strike out The polymerized material was stripped of monomer by heating at 239 F. for 16 hours; line 21, for nor read -no-; column 6, line 34:, for reaching read -reacting; line 36, for sodium potassium hydroxide read -sodium or potassium hydroxide.
Signed and sealed this 28th day of April 1959.
[SEAL] Attest T. B. MORROW, ROBERT C. WATSON,
Attestz'ng 0772067. Commissioner of Patents.
Claims (1)
1. A HYDROCARBON OIL CONTAINING A MINOR AMOUNT SUFFICIENT TO INHIBIT FORM OF A HOMOPOLYMER OF A MONOVINYLALKOXYSILANE HAVING A MOLECULAR WEIGHT OF AT LEAST ABOUT 325 WHICH HAD BEEN POLYMERIZED THROUGH THE VINYL GROUP.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BE544303D BE544303A (en) | 1955-01-18 | ||
US482657A US2862885A (en) | 1955-01-18 | 1955-01-18 | Foam inhibition in hydrocarbon oils |
FR1146658D FR1146658A (en) | 1955-01-18 | 1956-01-12 | Inhibition of foam in hydrocarbon oils |
GB1358/56A GB814200A (en) | 1955-01-18 | 1956-01-16 | Foam inhibition in oils |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US482657A US2862885A (en) | 1955-01-18 | 1955-01-18 | Foam inhibition in hydrocarbon oils |
Publications (1)
Publication Number | Publication Date |
---|---|
US2862885A true US2862885A (en) | 1958-12-02 |
Family
ID=23916911
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US482657A Expired - Lifetime US2862885A (en) | 1955-01-18 | 1955-01-18 | Foam inhibition in hydrocarbon oils |
Country Status (4)
Country | Link |
---|---|
US (1) | US2862885A (en) |
BE (1) | BE544303A (en) |
FR (1) | FR1146658A (en) |
GB (1) | GB814200A (en) |
Cited By (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4028070A (en) * | 1974-04-11 | 1977-06-07 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Method of recovering ethylene oxide |
EP0083044A2 (en) * | 1981-12-30 | 1983-07-06 | Bayer Ag | Anti-foam agent |
US4460380A (en) * | 1982-12-27 | 1984-07-17 | Exxon Research & Engineering Co. | Water shedding agents in distillate fuel oils |
US4537677A (en) * | 1984-11-05 | 1985-08-27 | Dow Corning Corporation | Oil emulsions of fluorosilicone fluids |
US4541838A (en) * | 1984-12-24 | 1985-09-17 | Ethyl Corporation | Fuel compositions |
US4690688A (en) * | 1985-03-29 | 1987-09-01 | Dow Corning, Ltd. | Foam control |
US4711714A (en) * | 1984-06-30 | 1987-12-08 | The British Petroleum Company P.L.C. | Method for the separation of gas from oil |
US5296132A (en) * | 1992-10-06 | 1994-03-22 | Betz Laboratories, Inc. | High temperature hydrocarbon defoamer composition and method |
WO1994019430A1 (en) * | 1993-02-26 | 1994-09-01 | Exxon Chemical Patents Inc. | Oil additives and compositions |
US5389299A (en) * | 1992-10-06 | 1995-02-14 | Betz Laboratories, Inc. | High temperature hydrocarbon defoamer composition and method |
US5397367A (en) * | 1993-11-19 | 1995-03-14 | Dow Corning Corporation | Middle distillate hydrocarbon foam control agents from cross-linked organopolysiloxane-polyoxyalkyenes |
US5435811A (en) * | 1993-11-19 | 1995-07-25 | Dow Corning Corporation | Middle distillate hydrocarbon foam control agents from alkymethylsiloxanes |
US5667669A (en) * | 1996-03-22 | 1997-09-16 | Betzdearborn Inc. | Methods for inhibiting foam |
US5800738A (en) * | 1996-06-13 | 1998-09-01 | Betzdearborn Inc. | Methods for inhibiting foam in crude oils |
US6083998A (en) * | 1998-04-24 | 2000-07-04 | Betzdearborn Inc. | Defoamer and methods of use thereof |
US20040015032A1 (en) * | 2002-07-16 | 2004-01-22 | Ramaswamy Perumangode Neelakantan | Method for reducing foam in a primary fractionator |
US20050224394A1 (en) * | 2002-06-26 | 2005-10-13 | Dorf Ketal Chemicals India Pvt. Ltd. | Method of removal of carbonyl compounds along with acid gases from cracked gas in ethylene process |
US10213708B2 (en) | 2013-12-06 | 2019-02-26 | Instituto Mexicano Del Petroleo | Formulations of homopolymers based on alkyl acrylates used as antifoaming agents in heavy and super-heavy crude oils |
US10221349B2 (en) | 2015-07-17 | 2019-03-05 | Instituto Mexicano Del Petroleo | Formulations of copolymers based on alkyl acrylates used as defoamers of heavy and super-heavy crude oils |
US10982031B2 (en) | 2016-03-31 | 2021-04-20 | Instituto Mexicano Del Petroleo | Formulation of terpolymers based on alkyl acrylates employed as antifoaming of gasified heavy and super-heavy crude oils |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2533700A (en) * | 1946-09-06 | 1950-12-12 | Standard Oil Co | Nonfoaming lubricant composition |
-
0
- BE BE544303D patent/BE544303A/xx unknown
-
1955
- 1955-01-18 US US482657A patent/US2862885A/en not_active Expired - Lifetime
-
1956
- 1956-01-12 FR FR1146658D patent/FR1146658A/en not_active Expired
- 1956-01-16 GB GB1358/56A patent/GB814200A/en not_active Expired
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2533700A (en) * | 1946-09-06 | 1950-12-12 | Standard Oil Co | Nonfoaming lubricant composition |
Cited By (24)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4028070A (en) * | 1974-04-11 | 1977-06-07 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Method of recovering ethylene oxide |
EP0083044A2 (en) * | 1981-12-30 | 1983-07-06 | Bayer Ag | Anti-foam agent |
EP0083044A3 (en) * | 1981-12-30 | 1984-12-12 | Bayer Ag | Anti-foam agent |
US4460380A (en) * | 1982-12-27 | 1984-07-17 | Exxon Research & Engineering Co. | Water shedding agents in distillate fuel oils |
US4711714A (en) * | 1984-06-30 | 1987-12-08 | The British Petroleum Company P.L.C. | Method for the separation of gas from oil |
US4537677A (en) * | 1984-11-05 | 1985-08-27 | Dow Corning Corporation | Oil emulsions of fluorosilicone fluids |
US4541838A (en) * | 1984-12-24 | 1985-09-17 | Ethyl Corporation | Fuel compositions |
US4690688A (en) * | 1985-03-29 | 1987-09-01 | Dow Corning, Ltd. | Foam control |
US5296132A (en) * | 1992-10-06 | 1994-03-22 | Betz Laboratories, Inc. | High temperature hydrocarbon defoamer composition and method |
US5389299A (en) * | 1992-10-06 | 1995-02-14 | Betz Laboratories, Inc. | High temperature hydrocarbon defoamer composition and method |
WO1994019430A1 (en) * | 1993-02-26 | 1994-09-01 | Exxon Chemical Patents Inc. | Oil additives and compositions |
US5435811A (en) * | 1993-11-19 | 1995-07-25 | Dow Corning Corporation | Middle distillate hydrocarbon foam control agents from alkymethylsiloxanes |
US5397367A (en) * | 1993-11-19 | 1995-03-14 | Dow Corning Corporation | Middle distillate hydrocarbon foam control agents from cross-linked organopolysiloxane-polyoxyalkyenes |
US5667669A (en) * | 1996-03-22 | 1997-09-16 | Betzdearborn Inc. | Methods for inhibiting foam |
US5800738A (en) * | 1996-06-13 | 1998-09-01 | Betzdearborn Inc. | Methods for inhibiting foam in crude oils |
US6083998A (en) * | 1998-04-24 | 2000-07-04 | Betzdearborn Inc. | Defoamer and methods of use thereof |
US6448298B1 (en) | 1998-04-24 | 2002-09-10 | Betzdearborn, Inc. | Defoamer and methods of use thereof |
US20050224394A1 (en) * | 2002-06-26 | 2005-10-13 | Dorf Ketal Chemicals India Pvt. Ltd. | Method of removal of carbonyl compounds along with acid gases from cracked gas in ethylene process |
US7575669B2 (en) | 2002-06-26 | 2009-08-18 | Dorf Ketal Chemicals, Llc | Method of removal of carbonyl compounds along with acid gases from cracked gas in ethylene process |
US20040015032A1 (en) * | 2002-07-16 | 2004-01-22 | Ramaswamy Perumangode Neelakantan | Method for reducing foam in a primary fractionator |
US7906012B2 (en) | 2002-07-16 | 2011-03-15 | Dorf Ketal Chemicals India Pvt. Ltd. | Method for reducing foam in a primary fractionator |
US10213708B2 (en) | 2013-12-06 | 2019-02-26 | Instituto Mexicano Del Petroleo | Formulations of homopolymers based on alkyl acrylates used as antifoaming agents in heavy and super-heavy crude oils |
US10221349B2 (en) | 2015-07-17 | 2019-03-05 | Instituto Mexicano Del Petroleo | Formulations of copolymers based on alkyl acrylates used as defoamers of heavy and super-heavy crude oils |
US10982031B2 (en) | 2016-03-31 | 2021-04-20 | Instituto Mexicano Del Petroleo | Formulation of terpolymers based on alkyl acrylates employed as antifoaming of gasified heavy and super-heavy crude oils |
Also Published As
Publication number | Publication date |
---|---|
FR1146658A (en) | 1957-11-14 |
BE544303A (en) | 1900-01-01 |
GB814200A (en) | 1959-06-03 |
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